Catalytic AsymmetricRearrangement of Azoalkene-DerivedSulfonium Ylides via Remote Chirality Control

The [2,3]-sigmatropic rearrangement has been widely utilized to construct C–S bonds. Herein, we report an enantioselective, intermolecular, and noncarbenoid [2,3]-sigmatropic rearrangement of sulfonium ylides using azoalkenes. This process features a broad substrate scope, high efficiency, and excellent enantioselectivity, achieving yields of up to 99% and an enantiomeric excess (ee) of up to 96%. Furthermore, the protocol demonstrated good scalability.